Hydrogen is being pursued as clean fuel for future applications particularly, by using fuel cells, in transportation sector. Four major issues need to be addressed for hydrogen energy utilization include; production of hydrogen, delivery to fueling station, onboard storage on vehicle and utilization of hydrogen for power generation. Hydrogen storage and supply is therefore an important aspect of successful utilization of hydrogen energy. Presently several methods used for hydrogen storage include, pressurization, liquefaction, physical adsorption on various adsorbents including carbon nano-tubes, metal hydrides, alanates, hybrid hydrides and chemical hydrides. All these methods of hydrogen storage except chemical hydrides besets with disadvantage that either a particular method is having low weight basis capacity of hydrogen storage or volumetric capacity is lower.
Hydrogen containing chemicals which are useful for storage of hydrogen include methanol, ammonia and cycloalkanes. At standard temperature and pressure all these are in liquid phase and therefore provide advantage of possibility of using existing infrastructure used for gasoline. The hydrogen storage capacities of these may range in the scale of 6 to 8 wt %. The supply of hydrogen through liquid organic hydrides (LOH) using catalytic reaction pair of dehydrogenation of cycloalkanes such as methylcyclohexane, cyclohexane and decalin; and hydrogenation of corresponding aromatics would be a useful process for supply of hydrogen to PEM (proton exchange membrane) fuel cells and is expected to overcome the disadvantages of other hydrogen storage systems. This would be the most promising methods to store, transport and supply with in-situ generation of hydrogen due to several advantages associated with this system which include; CO free hydrogen at fuelling stations, reversible catalytic reactions, recyclable reactants and products, relatively high hydrogen contents (6-8% on weight basis and about 60-62 kg H2/m3 on volume basis) and no CO2 generation as in the case of steam reforming of hydrocarbons. Due to high boiling points of cycloalkanes, the present infrastructure such as oil tankers and tank lorries can be used for the long-term storage and long-distance transportation of hydrogen in the form of LOH. Particularly, the approach is expected to be most useful to transport the hydrogen from centralized generation facilities to fuelling stations.
Reference may be made to U.S. Pat. No. 5,198,207, wherein doping of magnesium with other metals such as aluminium, indium, iron, etc. has been used to catalyze the hydrogenation of magnesium. U.S. Pat. No. 5,198,207 suggests adding to the magnesium a small amount of magnesium hydride, typically higher than 1.2% by weight, in order to catalyze the hydrogenation of magnesium at temperatures above 250° C. under a pressure ranging between 5 and 50 bars. According to what is disclosed in the patent, this technique called “autocatalysis” permits to complete the hydrogenation in a period of time longer than 7 hours. The drawback of this method is requirement of relatively high pressures for hydrogenation.
Reference may be made to Patent Application US20010014309, wherein a hydrogen storage composition having a hydrogenated state and a dehydrogenated state has been described; the hydrogenated state comprises a hydride composition of lithium and an element M which forms a hydride, for example Be or Mg, an element which forms a compound or solid solution with lithium, e.g. C, B or Zn, or a mixture thereof; there are thus provided reversible Li-based hydrides of high hydrogen capacity. The drawback of this method is that longer equilibrium periods are required. This drawback has been overcome in this invention by using instantaneous catalytic reaction for hydrogenation and dehydrogenation.
Several patents describe the inventions related to Mg-based alloys for storage of hydrogen. Reference maybe made to International patent application WO 99/2422, wherein a process for the preparation of a nano-composite for the storage of hydrogen comprising the step of subjecting to an intensive mechanical grinding a magnesium hydride or an hydride of a Mg-based compound and one or more elements or compounds that are known to absorb hydrogen and to be not miscible with magnesium during grinding is disclosed. Indeed, this process requires the use of magnesium hydride as starting material. The drawback of this method is relatively low capacity for hydrogen and long mixing times for equilibrium.
Use of alanates has been reported for hydrogen storage. Reference maybe made to Patent Application No US20030053948, Patent application PCT/WO 97/03919, U.S. Pat. No. 3,138,433 and Patent Application No US20050032641, wherein alanates have been used for hydrogen storage. The drawbacks of these methods are that the hydrogen capacity of all these methods described are relatively low and requires longer time of equilibrium for hydrogenation.
Reference may be made to U.S. Pat. No. 3,759,823, which describes a hydrocarbon conversion catalysts of 0.01-10% wt metal on a refractory support contains platinum and a second metal which forms a solid with Pt, the atomic amount of each being equivalent to amounts forming ordered alloy structures. The second metal may be Co, Ni, Fe, Cu, Sn, Pd, or Cd and preferably there is at least 45 atomic percent Pt. the catalysts may be prepared by known impregnation or ion exchange techniques and are preferably reduced before use at 250-600° C. The preferred use is dehydrocyclisation or dehydrogenation of C3-C25 hydrocarbons, particularly the catalytic reforming of 15-204° C., boiling range petroleum fractions.
Reference may be made to U.S. Pat. No. 4,567,033, which describes a method “freeing” molecular hydrogen from methylcyclohexane by its dehydrogenation to toluene at 316° C. The required thermal input being supplied by combustion of a considerable portion of the by-product hydrogen.
Reference maybe made to U.S. Pat. No. 5,372,617, which describes an invention related to a type of hydrogen generation system wherein chemical hydrides in solid phase are used, e.g. granules, comprises a closed vessel for mixing chemical hydride powder together with water. The water is introduced into the vessel through an inlet. The vessel contains a mechanical stirring device to ensure adequate contact between the powder and the water, and to prevent the powder from clumping. The hydrogen gas is removed through an outlet in the vessel, and is supplied directly to the fuel cell. These systems tend to be inefficient since the stirring mechanism consumes energy, and increases the overall weight and complexity of the system. The reaction rate tends to be low, making the hydrogen generation unpredictable and thus hard to control. The systems also tend to be large and cumbersome.
Reference maybe made to U.S. Pat. No. 5,702,491, wherein the hydrogen generation system disclosed comprises a thermally isolated container for containing chemical hydride, a pre-heater to heat the chemical hydride to a predetermined temperature before the chemical hydride is hydrolyzed, a water pipe to supply water into the container to generate hydrogen. The drawback is that this system entails adiabatic arrangement and heating devices, hence results in lower energy efficiency and complicated structure.
Reference may be made to U.S. Pat. No. 5,833,934, discloses a cartridge-type reactor comprising a storage compartment for storing chemical hydride particles, a water absorbent material for retaining water and a water distribution tube for introducing water into the mass of chemical hydride particles. The drawback of the method is relatively low hydrogen content as compared to possible storage in cycloalkanes and irreversible dehydrogenation leading to no-recycling of the hydrides.
Another class of chemical hydrides reported in various prior arts is liquid organic hydride. Liquid organic hydrides such as cycloalkanes are potential hydrogen storage materials due to its high hydrogen content both on volume basis and weight basis. Reference maybe made to U.S. Pat. No. 6,074,447, wherein dehydrogenation of methylcyclohexane, decalin, dicyclohexyl, and cyclohexane to toluene, naphthalene, biphenyl and benzene, respectively, in the presence of particular iridium based molecular complex catalyst at preferably 190° C. or higher is disclosed.
Reference may be made to Japanese Patent JP2001198469, describes hydrogen storage and supply system wherein a catalyst containing at least one metal selected from Ni, Pd, Pt, Rh, Ir, Ru, Mo, Re, W, V, Os, Cr, Co and Fe having good activity for both hydrogenation of hydrogen storage body comprising an aromatic compound and dehydrogenation of a hydrogen supply body comprising the hydrogenated derivative of aromatic compound. The catalysts used are monometallic catalysts which results into relatively lower activity and stability. The metal support interaction is not used for efficient selective dehydrogenation.
Reference may be made to Japanese Patent JP2002134141 describes the equipment used for dehydrogenation of liquid organic hydrides with arrangement for intermittent supply of prescribed amount of liquid organic hydride and a product separator for separating hydrogen from other products.
Reference maybe made to Japanese patents No. JP20001110437 and JP2002134141, wherein use of benzene, toluene, xylene, mesitylene, naphthalene, anthracene, biphenyl, phenanthrene and their alkyl derivatives are possible aromatic substrates used as a means of producing hydrogen for fuel cells has been described. The catalyst used is Pt supported on high surface area substrate.
Chemical hydrides such as NaBH4, LiBH4, KBH4, RbBH4 are reported for storage of hydrogen. Reference maybe made to United States Patent Application 20030014917, wherein a hydrogen generation system comprises: a storage means for storing a chemical hydride solution; a reactor containing a catalyst; a means for supplying the chemical hydride solution from the said storage means to the said reactor so that the chemical hydride solution reacts to generate hydrogen in the presence of the catalyst; and a second supplying means for continuously supplying the solvent of the said solution to the chemical hydride solution during the reaction. The energy system comprises the hydrogen generation system, a fuel cell for generating electricity and water from hydrogen and an oxidant, and a means for recovering the water generated in the said fuel cell and supplying the said water to the chemical hydride solution during the reaction. The chemical hydride hydrogen generation system here uses the solute, which is selected from the group consisting of: NaBH4, LiBH4, KBH4, RbBH4. Generally, chemical hydride reacts with water in the presence of a catalyst to generate hydrogen.
Reference may be made to US Patent Application 20030091876 and US Patent Application 20030091879, wherein the chemical hydride considered are NaBH4, LiBH4, KBH4, RbH4, NH3BH3 and combination with water, further include alkaline additives such as LiOH, KOH, NaOH. A chemical hydride hydrogen generation system and an energy system incorporating the same are provided. The hydrogen generation system has: storage means for storing a chemical hydride solution; a reactor containing a catalyst; and a pump for supplying the chemical hydride solution from the storage means to the reactor so that the chemical hydride solution reacts to generate hydrogen in the presence of the catalyst. The hydrogen is supplied to a fuel cell stack. Additionally, a heat transfer circuit is provided including a heat transfer fluid that is circulated through the cooling channels of the fuel cell stack to effect heating thereof on startup, and cooling once the operating temperature is reached.
Reference maybe made to U.S. Patent Application 20030099595, wherein a process for enhancing the kinetics of hydrogenation/dehydrogenation of complex chemical hydrides using mechanomixing and/or mechanomilling is disclosed. The mechano-mixing makes hydrogenation/dehydrogenation of complex chemical hydrides reversible at much reduced temperature and pressure. The mechanomilling claimed to reduce particle size or grain size of the decomposition byproducts, further increasing surface area and intimate contact of the byproducts. In this invention, complex chemical hydride is proposed to be utilized as a reversible hydrogen storage media for various applications such as transportation, including fuel cells. The drawback of the method is mechano-mixing requires long periods and is also energy intensive.
Reference may be made to US Patent Application 20040199039, discloses a method for the gas phase dehydrogenation of hydrocarbons in narrow reaction chambers and integrated reactors. Examples of hydrocarbons for dehydrogenation include propane and isobutane to propylene and isobutene, respectively. Reported in the publication are articles by Jones, et al, and Besser, et al, who describe the gaseous dehydrogenation of cyclohexane in a microreactor. Jones, et al employs a reported feed pressure of 150 kPa and an exit pressure of 1 Pa.
Reference maybe made to U.S. Pat. No. 6,802,875, discloses a hydrogen supply system for a fuel cell which includes a fuel chamber for storing a fuel such as isopropyl alcohol, methanol, benzene, methylcyclohexane, and cyclohexane, a catalytic dehydrogenation reactor, a gas-liquid separation device wherein byproduct is liquefied and separated from the gaseous dehydrogenation reaction product, and a recovery chamber for the hydrogen and dehydrogenated byproduct.
Reference maybe made to US Patent Application No. 20040074759, wherein a process is disclosed for the catalytic reaction of organic compounds, in which the organic compounds are contacted with a catalyst comprising an interstitial metal hydride, having a reaction surface, to produce a catalyst-organic compound mixture. Energy is applied and monatomic hydrogen is produced at the reaction surface of the interstitial metal hydride. The organic compounds are reacted with the monatomic hydrogen. Reactions accomplished by this process include petroleum hydrocracking and hydrotreating processes. The method's performance can be further enhanced using radio frequency (RF) or microwave energy. The drawback of the method is that it requires to produce a catalysts-organic compound mixture thereby poses difficulties in separation of the catalysts and catalysts requirement is generally higher reducing the effective hydrogen storage capacity of the system.
Reference maybe made to U.S. Patent Application 20050002857, wherein processes are provided for the storage and release of hydrogen by means of a substantially reversible catalytic hydrogenation of extended pi-conjugated substrates which include large polycyclic aromatic hydrocarbons, polycyclic aromatic hydrocarbons with nitrogen heteroatoms, polycyclic aromatic hydrocarbons with oxygen heteroatoms, polycyclic aromatic hydrocarbons with alkyl, alkoxy, nitrile, ketone, ether or polyether substituents, pi-conjugated molecules comprising five membered rings, piconjugated molecules comprising six and five membered rings with nitrogen or oxygen hetero atoms, and extended pi-conjugated organic polymers. The hydrogen, contained in the at least partially hydrogenated form of the extended pi-conjugated system, can be released for use by a catalytic dehydrogenation of the latter in the presence of a dehydrogenation catalyst which can be effected by lowering the hydrogen gas pressure, generally to pressures greater than 0.1 bar or raising the temperature to less than 250° C. or less, or by a combination of these two process parameters. The catalysts for hydrogenation is metal selected from group 4, 5, 6 and 8, 9, 10 of the periodic table according to the International Union of Pure and Applied Chemistry. The drawbacks of the method are the process of hydrogenation is carried out at a relative high hydrogen partial pressure and during dehydrogenation its required to maintain partial pressure of hydrogen above 0.1 bar. Also the hydrogen storage capacity obtained was in the range of 1 to 4.7% by weight which is relatively low for economical use of these chemicals. The low hydrogen storage capacity was due to addition of catalyst in reactant itself (particularly 2.3 wt % for pyrene+catalyst and 3.5 wt % for coronene+catalyst) would put weight penalties on transportation. The requirement of means of catalyst separation such as extraction with chloroform is yet another drawback of this system. A high pressure and longer period is required in milling operation. Further in case of some of the pi-conjugated compounds there is irreversible hydrogenation to isomers e.g. in the case of coronene the irreversible hydrogenated product consists of mass 318 isomer upto 20% making the said compound unsuitable for reuse and recycle.
Reference may be made to U.S. Patent no. 20050013767, which discloses a method of delivering a reversible hydrogen storage fuel to a mobile or stationary fuel source. Wherein the patent application describes a fueling process comprising: placing a dispenser comprising a first conduit having an orifice for dispensing a first liquid comprising an at least partially hydrogenated pi-conjugated substrate and a second conduit having an orifice for retrieving a second liquid comprising a pi-conjugated substrate in flow communication with a first compartment and a second compartment; transferring a portion of the first liquid residing in the first compartment into a hydrogen generator and contacting the portion of the stored first liquid with a dehydrogenation catalyst under dehydrogenation conditions sufficient to provide hydrogen and the second liquid; transferring at least a portion of the second liquid into the second compartment; transferring the first liquid through the first conduit into the first compartment and transferring the second liquid through the second conduit. Wherein the pi-conjugated substrate is an extended pi-conjugated substrate selected from the group consisting of extended polycyclic aromatic hydrocarbons, extended piconjugated substrates with nitrogen heteroatoms, extended pi-conjugated substrates with heteroatoms other than nitrogen, pi-conjugated organic polymers and oligomers, ionic pi-conjugated substrates, piconjugated monocyclic substrates with multiple nitrogen heteroatoms, pi-conjugated substrates with at least one triple bonded group, a pitch, and any combination of two or more of the foregoing.
Reference may be made to U.S. Pat. No. 7,101,530, which describes processes provided for the storage and release of hydrogen by means of substantially reversible catalytic hydrogenation of extended pi conjugated substrate which include large polycyclic aromatic hydrocarbons, polycyclic aromatic hydrocarbon with nitrogen heteroatoms, polycyclic aromatic hydrocarbon with oxygen heteroatoms, polycyclic aromatic hydrocarbon with alkyl, alkoxy, ketone, ether or polyether substituent, pi conjugated molecule comprising 5 membered rings, pi conjugated molecule comprising six and five membered rings with nitrogen or oxygen heteroatoms, and extent pi conjugated organic polymers. The hydrogen, contained in the at least partially hydrogenated form of the extended pi conjugated system, can be facilely released for the use by a catalytic dehydrogenation of the latter in presence of dehydrogenation catalyst which can be effected by lowering hydrogen gas pressure, generally to pressure greater than 0.1 bar or raising the temperature less than 250° C. or less, or by a combination of these two process parameters.
Reference may be made to US Patent Application No. 20060143981, which describes an improved process for the storage and delivery of hydrogen by the reversible hydrogenation/dehydrogenation of an organic compound wherein the organic compound is initially in its hydrogenated state. The improvement in the route to generating hydrogen is in the dehydrogenation step and recovery of the dehydrogenated organic compound resides in the following steps: introducing a hydrogenated organic compound to a microchannel reactor incorporating a dehydrogenation catalyst; effecting dehydrogenation of said hydrogenated organic compound under conditions whereby said hydrogenated organic compound is present as a liquid phase; generating a reaction product comprised of a liquid phase dehydrogenated organic compound and gaseous hydrogen; separating the liquid phase dehydrogenated organic compound from gaseous hydrogen; and, recovering the hydrogen and liquid phase dehydrogenated organic compound.
Reference may be made to US Patent Application No. 20100010280 (Catalysts for dehydrogenation of hydrocarbons, 2010) wherein a stationary or fluid bed dehydrogenation catalyst containing an alumina carrier, with chromium and alkali metals consisting of only sodium and potassium, added as promoters is described. The resultant catalyst is demonstrated for dehydrogenation of hydrocarbons.
Reference may be made to P. Taube, M. A. Taube (Liquid organic carrier of H2 as a fuel for automobiles. Adv Hydrogen Energy volume 2, 1981 page no. 1077 to 1082) wherein dehydrogenation of methylcyclohexane was reported for seasonal storage of energy through storage and supply of hydrogen using Pt based catalysts.
Reference maybe made to Journal “R. W. Coughlin, K. Kawakami and A. Hasan (Activity, yield patterns, and coking behavior of Pt and PtRe catalysts during dehydrogenation of methylcyclohexane: I. In the absence of sulfur, Journal of Catalysis Vol. 88, 1984, page numbers 150 to 162) wherein Pt and Pt—Re catalyst has been reported for dehydrogenation of methylcyclohexane to produce hydrogen.
Reference maybe made to Journal “K Jouthimurugesan, S Bhatla, R. D. Srivastava (Kinetics of dehydrogenation of methylcyclohexane over a platinum-rhenium-alumina catalyst in the presence of added hydrogen, Industrial Engineering Chemistry Fundamentals 24(4), 1985 page number 433) wherein kinetics of dehydrogenation of methylcyclohexane over a Pt—Re/alumina catalyst in the presence of added hydrogen has been reported.
Reference may be made to Journal “N. F. Grünenfeldera and Th. H. Schucan (Seasonal storage of hydrogen in liquid organic hydrides: description of the second prototype vehicle, International Journal of Hydrogen Energy, volume 14, issue 8, 1989, page no. 579 to 586)” wherein The MTH-system (methyl cyclohexane, toluene and hydrogen) has been proposed for the seasonal storage of electricity. It consists of two closed loops: in the outer loop hydrogen is produced by electrolysis of water and later burned to give water again. In the inner loop the hydrogen is combined with toluene to give methyl cyclohexane. In this form the energy can be easily stored, transported and finally used throughout the year. At the moment of end use the hydrogen is liberated by splitting the methyl cyclohexane into hydrogen and toluene, and the toluene is recharged with hydrogen later. The most appropriate application of the seasonally stored hydrogen seems to be its use as fuel for heavy vehicles in combustion engines of fuel cells. The exhaust gas of a combustion engine powered by hydrogen consists of water vapour, N2 and NOx. There are no emissions of carbohydrates, carbon monoxide, carbon dioxide or dust particles. The system thus constitutes an important contribution to the protection of the environment. The on-board splitting reaction of methyl cyclohexane to toluene and hydrogen as well as its combination with the hydrogen-fueled combustion engine have been realized and investigated in full scale at our institute. In the present paper we describe the results obtained with the second prototype MTH 2 and we sketch the perspectives for the near future.
Reference may be made to Journal “J. K. Ali, E. J. Newson’ and D. W. T. Rippin (Exceeding equilibrium conversion with a catalytic membrane reactor for the dehydrogenation of methylcyclohexane, Chemical Engineering Science. Volume 49, Issue No. 13. Page no. 2129 to 2134, 1994)” where in catalytic membrane reactor containing a tubular palladium-silver (Pd—Ag) membrane sealed in the centre to separate in situ the hydrogen produced, was used to exceed equilibrium limitations in the dehydrogenation of methylcyclohexane. A sulphide, monometallic, noble metal catalyst produced higher than equilibrium yields of toluene and hydrogen from methylcyclohexane at economically viable throughputs. Experiments in the membrane reactor in the temperature range of 573-673 K, pressure. Range of 0.5-2.0 MPa and liquid hourly space velocity range of 2-12 volume feed/h/reactor volume showed conversions up to 4 times higher than equilibrium values after 300 h onstream and repeated temperature cycling. Exceeding equilibrium was due to the selective permeation of one of the reaction products, i.e. hydrogen, through the membrane. Reactor axial temperature profiles for the reaction with and without a membrane showed that the. total amount of catalyst is more efficiently utilized in the membrane reactor.
Reference may be made to Journal “Scherer, G. W. et al. (International J. hydrogen energy, 1999, 24, 1157)” which disclose the possibility of storing and transporting hydrogen for energy storage via the catalytic gas phase hydrogenation and the gas phase, high temperature, dehydrogenation of common aromatic molecules, e.g., benzene and toluene over Pt/activated carbon catalysts.
Reference may be made to R. O. Loufty and E. M. Vestker in “Investigation of Hydrogen Storage in Liquid organic hydrides” proceedings of the international hydrogen energy forum 2000, Munich Germany, 2000; pages 335-340, wherein they have reported the dehydrogenation of decaline in a membrane reactor where the very low conversion (15%) of decaline, even at 300° C. is greatly enhance by the selective separation of hydrogen by the membrane and its removal from the reactor.
Reference maybe made to Journal “Nobuko Kariya, Atsushi Fukuoka, and Masaru Ichikawa (Efficient evolution of hydrogen from liquid cycloalkanes over Pt-containing catalysts supported on active carbons under “wet-dry multiphase conditions, Applied Catalysis A: General, 233 page 29, 2002)” wherein evolution of hydrogen is reported in the dehydrogenation of cycloalkanes such as cyclohexane, methylcyclohexane, and decalin over Pt catalyst supported on active carbon (AC) under “wet-dry multiphase conditions”. Formation rate of hydrogen was largely dependent on reaction conditions such as reactant/catalyst ratio, temperature, and support. The addition of second metals such as Mo, W, Re, Rh, Ir, and Pd on the carbon-supported Pt catalysts reported to result in enhanced dehydrogenation rate due to the promotion of C—H bond cleavage and/or desorption of aromatic products. A physical mixture of Pt/AC and Pd/AC catalysts exhibits higher activities than the monometallic Pt/AC catalyst owing to the synergistic effects of spillover, migration, and recombination of hydrogen over Pt and Pd catalysts.
Reference maybe made to Journal “Shinya Hodoshima, Hiroshi Arai and Yasukazu Saito (Liquid-film-type catalytic decalin dehydrogeno-aromatization for long-term storage and long-distance transportation of hydrogen, International Journal of Hydrogen Energy, Vol. 28, page numbers 197 to 204, 2003)” describing liquid film-type catalytic decalin dehydrogeno-aromatization for long-term storage and long-distance transportation of hydrogen using catalyst Pt/C, Pt—Ir/C and Pt—W/C.
Reference maybe made to Shinya Hodoshima, Hiroshi Arai, Shigeki Takaiwa, Yasukazu Saito (Catalytic decalin dehydrogenation/naphthalene hydrogenation pair as a hydrogen source for fuel-cell vehicle, International Journal of Hydrogen Energy, Vol. 28, page numbers 1255 to 1262, 2003) describing Catalytic decalin dehydrogenation/naphthalene hydrogenation pair as a hydrogen source for fuel-cell vehicle using catalyst Pt/C and Pt—W/C.
Reference maybe made to Journal “Nobuko Kariya, Atsushi Fukuoka, Tadashi Utagawa, Masashi Sakuramoto, Yasushi Goto and Masaru Ichikawa (Efficient hydrogen production using cyclohexane and decalin by pulse-spray mode reactor with Pt catalysts, Applied Catalysis A: General Vol. 247, 2003 page number 247)”, wherein highly efficient production of hydrogen without CO2 emission is reported in the dehydrogenation of cyclic hydrocarbons under a non-steady spray pulse operation over supported Pt and Pt-M (M=Re, Rh, Pd) catalysts. Cyclohexane, methylcyclohexane, tetralin and decalin were dehydrogenated by the Pt-containing catalysts supported on thin active carbon cloth sheets and alumite (anodized aluminum) plates. Production rate of hydrogen under the spray pulse mode is reported to be higher than the conventional batch-type liquid phase reaction and the steady state gas phase reaction in the flow system. Production rate of hydrogen was dependent on the rate of reactant feed, the reaction temperature, and the support. Retardation by products adsorbed on the catalysts was negligible under the spray-pulse operation.
Reference maybe made to Journal “Rajesh B. Biniwale, Nobuko Kariya, and Masaru Ichikawa (Dehydrogenation of Cyclohexane Over Ni Based Catalysts Supported on Activated Carbon using Spray-pulsed Reactor and Enhancement in Activity by Addition of a Small Amount of Pt, Catalysis Letters Vol. 105, Nos. 1-2, November, 2005 page numbers 83 to 87)”, wherein dehydrogenation of cyclohexane over Ni based catalysts supported on activated carbon using spray-pulsed reactor and enhancement in activity by addition of a small amount of Pt is reported for hydrogen storage and supply application.
Reference maybe made to Journal “Shinya Hodoshima, Shigeki Takaiwa, Atsushi Shono, Kazumi Satoh and Yasukazu Saito (Hydrogen storage by decalin/naphthalene pair and hydrogen supply to fuel cells by use of superheated liquid-film-type catalysis, Applied Catalysis A: General Vol. 283, 2005 page numbers 235 to 242)” wherein hydrogen storage by decalin/naphthalene pair and hydrogen supply to fuel cells by use of superheated liquid-film-type catalysis and Pt/C catalysts is described.
Reference maybe made to Journal “Shinya Hodoshima, Hiroaki Nagata and Yasukazu Saito (Efficient hydrogen supply from tetralin with superheated liquid-film-type catalysis for operating fuel cells, Applied Catalysis A: General Vol. 292, 2005 page numbers 90 to 96)” reports efficient hydrogen supply from tetralin with superheated liquid-film-type catalysis and using catalysts namely Ni/C, Ru/C and Ni—Ru for operating fuel cells.
Reference maybe made to Journal “Yoshimi Okada, Eiji Sasaki, Eiji Watanabe, Shinji Hyodo and Hiroaki Nishijima (Development of dehydrogenation catalyst for hydrogen generation in organic chemical hydride method, International Journal of Hydrogen Energy, Vol. 31, 2006 page numbers 1348 to 1356) wherein dehydrogenation of methylcyclohexane has been reported on K—Pt/Al2O3 catalyst when heated near to 320° C.
Reference may be made to Journal “Sevim Yolcular, Ozden Olgun (Ni/Al2O3 catalysts and their activity in dehydrogenation of methylcyclohexane for hydrogen production, Catalysis Today volume 138, 2008, page no. 198 to 202)” wherein dehydrogenation of methylcyclohexane has been reported over Ni/Al2O3 catalysts in the temperature range of 653-713 K.
Reference may be made to Journal “Yasukazu Saitoa, Kiyoshi Aramakia, Shinya Hodoshima, Morihiro Saito, Atsushi Shono, Jun Kuwanoa and Katsuto Otake (Efficient hydrogen generation from organic chemical hydrides by using catalytic reactor on the basis of superheated liquid-film concept, Chemical Engineering Science volume 63 issue 20, 2008 page no. 4935 to 4941)” wherein under boiling and refluxing conditions for catalytic dehydrogenation of organic chemical hydrides (decalin, methylcyclohexane and others) in a batch-wise reactor, either suspended states with excess amounts of substrate or sand-bath states with its scarce amounts were found to be inferior generally to the so-called “liquid-film states” with adequate amount ratios of substrate to catalyst, where the catalyst-layer temperatures were superheated or raised higher than the boiling point, and, consequently, reactivities became more favorable at higher heating temperatures in contrast to the boiling suspended states. Equilibrium shifts due to reactive distillation were well demonstrated under boiling and refluxing conditions in naphthalene dehydrogenation. Moreover, desorption of hydrogen from the active sites to the bubble space was enhanced in the superheated liquid-film states, with large translational entropy endowed.
Reference may be made to Journal “Rajesh B. Biniwale, S. Rayalu, S. Devotta, M. Ichikawa (Chemical hydrides: A solution to high capacity hydrogen storage and supply, International Journal of Hydrogen Energy, Volume 33, Issue 1, January 2008, Pages 360-365)” wherein a review of various catalysts for dehydrogenation of cycloalkanes is reported. The catalysts include Pt, Ni supported on either activated carbon or alumite.
Reference may be made to Journal “Anshu Shukla, Priti Gosavi, Jayhshri Pande, Vanama Kumar, K. V. R. Chary, Rajesh Biniwale (Efficient hydrogen supply through catalytic dehydrogenation of methylcycklohexane over Pt/metal oxide catalyst, International journal of hydrogen energy, volume 35, 2010, page no. 4020-4026)” wherein catalysts consisting of Pt supported on various metal oxide including La2O3, Al2O3, TiO2, ZrO2, CeO2, MnO2, Fe2O3 has been reported. A further Pt/LaNiO3 and Pt/La0.7Y0.3NiO3 catalyst has been reported for dehydrogenation of methylcyclohexane. However the activity of catalysts is relatively lower.
The literature available on the hydrogen storage and supply indicated the use of dehydrogenation of hydrogenated organic hydrocarbons for carrying hydrogen. Several other chemical hydrides are also reported. The literature appears to use the noble metal, particularly Pt as catalyst along with a few bimetallic catalysts such as Ni—Pt. Use of bimetallic catalysts for spillover, migration and recombination of abstracted H atoms for purpose of dehydrogenation of hydrogenated liquid organic compound is barely reported. The stability of catalyst in prior art is relatively lower. Further, in case of monometallic catalyst the selectivity towards dehydrogenation is lower.